JPH06123077A - Moisture-permeable water-proofing coated cloth - Google Patents

Abstract

PURPOSE:To obtain a coated cloth having excellent water-proofing performance, moisture-permeability and peeling resistance by coating a cloth with a solution of a synthetic polymer composed mainly of a polyurethane resin containing silicon dioxide having particle diameter smaller than a specific level and a compound having high affinity to the cloth. CONSTITUTION:A textile cloth of e.g. synthetic fiber is coated with a solution composed mainly of a polyurethane produced by uniformly dispersing >=1wt.% of nonporous fine powder of silicon dioxide having an average particle diameter of <=0.1mum, >=0.1wt.% of an isocyanate compound having high affinity to the textile cloth and >=5wt.% of a resin selected from polyamide resin, polyurethane resin and polyester resin. The coating layer is coagulated in wet state to obtain the objective moisture-permeable water-proofing coating cloth having a moisture- permeability of >=7,000g/m<2> 24hr, a water-pressure resistance of >=0.6kg/cm<2> and a peeling strength of >=2,000g/inch. A cloth suitable for raincoat, outerwear, etc., can be produced at a low cost by this process.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-permeable and waterproof coating cloth having good peeling resistance, which is used for various clothes such as rain clothes and outer clothes.

[0002]

2. Description of the Related Art It has been known that a moisture-permeable and waterproof cloth having a moisture-permeable membrane on the surface of the cloth has a porous moisture-permeable membrane and a non-porous material. In particular, those having a non-porous moisture permeable membrane are more excellent in washing resistance and abrasion resistance than porous membranes having continuous fine pores on the surface of the membrane capable of radiating water vapor of 1 to 3 μm. It is known as a damp and waterproof fabric, but the moisture permeability required for the fabric is often insufficient, and satisfactory performance cannot be obtained as a damp and waterproof fabric.

On the other hand, among those having a porous membrane having continuous fine pores, there are some which have both sufficient moisture permeability and waterproof performance, but as an actual windbreaker or other clothing. When sewn and subjected to a wear test, the film was rubbed by underwear and peeled off, or the film peeled off due to bending due to long-term movement, and the function as a moisture-permeable waterproof fabric was significantly reduced. There was a problem of doing.

In order to remedy this drawback, an isocyanate compound having a high affinity with the base cloth or the resin film is applied to the coating surface of the fiber base cloth before the formation of the resin film, so that the adhesion between the base cloth and the resin film is improved. Attempts have been made to improve the peeling strength, but the peeling strength of the film cannot be obtained, and the manufacturing process also has the drawback of increasing the number of processes for applying the chemicals to the fabric and increasing the processing cost. .

In order to remedy these drawbacks, the present inventors have disclosed in Japanese Patent Application No. 3-260971 a silicon dioxide fine powder having substantially no pores in a resin film and an average particle size of 0.1 μm or less. Was proposed, and relatively good results were obtained in terms of peeling resistance, but satisfactory results have not yet been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to obtain a moisture-permeable and water-proof coating fabric which is comparable in peel resistance of a resin film. Is.

[0007]

SUMMARY OF THE INVENTION The present invention achieves the above object and has the following configuration. That is, the present invention has a porous resin layer made of a synthetic polymer mainly composed of a polyurethane resin on a fiber cloth, and the silicon dioxide having substantially no pores and an average particle diameter of 0.1 μm or less in the resin layer. Containing 1% by weight or more of fine powder, 0.1% by weight or more of isocyanate compound, and 5% by weight or more of at least one kind of polyamide resin, polyurethane resin and polyester resin, 7,000 g / m ² / 24hrs
Water vapor transmission rate of more than 0.6 kg / cm ² and water pressure resistance of 200 or more
The gist of the present invention is a moisture-permeable waterproof coating fabric having a peel strength of 0 g / inch or more.

The present invention will be described in detail below.

The characteristic feature of the coated cloth of the present invention in the production is that of a synthetic polymer mainly composed of a polyurethane resin in a polar organic solvent solution, among silicon dioxide fine powder, an isocyanate compound and a polyamide resin, a polyurethane resin and a polyester resin. It is the point that it is manufactured by the so-called wet coating method in which at least one kind of resin is added and then it is dipped in water to form a resin film. This is to form a fine, highly moisture-permeable resin layer with a large number of pores on the fiber base cloth with strong adhesion without deteriorating the temperature.

The substantially non-porous silicon dioxide fine powder used in the present invention is generally a silicon dioxide obtained by a dry method such as a vapor-phase oxidation method of silicon halide, a combustion hydrolysis method of silicon halide, or an electric arc method. The fine powder obtained by the above method is a hydrophilic substance because it has a large number of silanol groups on the particle surface like other general silicon dioxide fine powders. In the present invention, silicon dioxide fine powder having a large number of silanol groups on the particle surface has sufficient effect, but this hydrophilic silicon dioxide fine powder is uniformly dispersed in a synthetic polymer solution mainly composed of polyurethane resin. Since the viscosity of the resin solution is likely to be thixotropic and tends to adsorb water as well, caution is required in the operation of the coating. In addition, the resin film obtained is hydrophilized, so from the viewpoint of water leakage. There are some disadvantages.

In order to make up for these drawbacks, silicon dioxide fine powder is used in the above fine powder to make the fine particle surface hydrophobic by reacting with silanol groups with substances such as trimethylchlorosilane, dimethyldichlorosilane, ethyl alcohol and isopropyl alcohol. It is effective to use this hydrophobic fine powder, because it does not become so thixotropic and the amount of adsorbed water is small, the stability of the substance itself is excellent, and it is advantageous in operation.

Further, the fine powder used in the present invention may be mainly fine powder of silicon dioxide, and also contains aluminum oxide, magnesium oxide and the like as impurities or a mixture, general fillers, pigments and the like. There is no problem even if it is done.

The silicon dioxide fine powder used in the present invention is
It means one containing 60% or more as a silicon dioxide component. The fine powder used has an average particle size of 0.1 μm.
It is necessary to be below, and if it is 0.05 μm or less, it is more preferable in terms of effects. Average particle size is 0.1 μm
If it is larger, the pore diameter of the fine pores of the moisture permeable membrane of the resulting coated fabric becomes too large, and the waterproof performance is deteriorated.

Further, it is necessary that the silicon dioxide fine powder is uniformly contained in the resin layer composed of a synthetic polymer mainly composed of polyurethane resin in an amount of 1% or more, and more preferably 3% or more. When it is less than 1%, the number of fine pores of the moisture permeable membrane of the obtained coated fabric is small, and high moisture permeability cannot be obtained.

The isocyanate compound used in the present invention is 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or a compound having 3 mol of these diisocyanates and active hydrogen (eg, trimethylolpropane, Examples thereof include triisocyanates obtained by addition reaction with 1 mol of glycerin and the like.

The above-mentioned isocyanates are in a form in which an isocyanate group is free, or in a form in which a block is dissociated by heat treatment after being stabilized by adding phenol, methylethylketoxime or the like. However, any of them may be used, and may be appropriately used depending on workability and application.

The amount of isocyanate compound used is
0.1 for synthetic polymers based on polyurethane resin
It is used in a proportion of from 10 to 10% by weight, preferably from 0.5 to 5% by weight. If the amount used is less than 0.1%, the adhesive force of the resin to the fiber base fabric will be poor, and conversely if it exceeds 10%, the texture will be hardened, which is not preferable.

As the polyamide resin, nylon 6,
Nylon 66, nylon 610, etc., or aliphatic polyamides such as N-methoxymethyl 66 nylon in which hydrogen of the amide group of nylon is methoxymethylated, and dimer acid-based polyamides represented by Versamide (trademark of Henkel Japan Ltd.) are listed. be able to.

Polyurethane resins include polyether polyols, polyester polyols, various grafted polyols, halogenated polyols, polyols having a diene chain, polycarbonate polyols, acrylic polyols and other polyols, and tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane. Examples thereof include a polymerization reaction product with an isocyanate such as diisocyanate and hexamethylene diisocyanate. In some cases, a diamine or the like may be used in combination as a cross-linking agent or a chain extender.

Polyester resins include ethylene glycol, diethylene glycol, propylene glycol, 1.4 butanediol, 1.6 hexanediol,
Examples include a polymerization reaction product of a diol such as polytetramethylene glycol and an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, adipic acid, sebacic acid or an aliphatic dicarboxylic acid, and a ring-opening polymerization product such as a lactone. The diol component and the acid component are selected so that the polymer is amorphous and are prepared so as to be dissolved in a polar organic solvent. For example, a polyester having a molecular weight of 20,000 is polymerized by using terephthalic acid and sebacic acid as acid components and ethylene glycol and neopentyl glycol as diol components.

Polyamide resin, polyurethane resin,
The amount of the polyester resin used is 5 to 100% by weight based on the synthetic polymer mainly composed of the polyurethane resin,
It is desirable to use it in a ratio of preferably 5 to 50% by weight. If the amount used is less than 5% by weight, the adhesive force of the resin to the fiber base cloth is poor, and if it exceeds 100% by weight, the texture is hardened, the resin film is deformed by heating, or the moisture permeability. Is decreased, or one of these disadvantages occurs, which is not preferable.

In the present invention, a polyamide-based resin, a polyurethane-based resin, or a polyester-based resin is appropriately selected and added to the polyurethane synthetic resin solution according to the material of the fiber base cloth used.

The fiber cloth used in the present invention includes polyamide synthetic fibers represented by nylon 6 and nylon 66, polyester synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile synthetic fibers,
Woven and knitted fabrics made of polyvinyl alcohol synthetic fibers, semi-synthetic fibers such as triacetate, or mixed fibers such as nylon 6 / cotton, polyethylene terephthalate / cotton, etc.
Nonwoven fabrics and the like can be mentioned.

In the present invention, the above-mentioned fiber cloth treated with a water repellent may be used. This is one means for preventing the penetration of the resin solution into the fabric. In this case, the water repellent may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment thereof may be a padding method, a spray method or the like which is generally performed. A known method may be used. When particularly good water repellency is required, a fluorine-based water repellent is used, for example, Asahi Guard 730 (Asahi Glass Co., Ltd., fluorine-based water repellent emulsion) is padded (squeezed) with a 5% aqueous dispersion. 35%)
After that, heat treatment at 160 ° C. for 1 minute may be performed.

In the coated cloth of the present invention, a synthetic polymer solution mainly composed of a polyurethane resin containing silicon dioxide fine powder and a compound having a high affinity for the fiber cloth is applied onto the above-mentioned fiber cloth by a wet coating method. The term "polyurethane resin-based synthetic polymer" as used herein means one containing 50 to 100% of a polyurethane component, and other synthetic polymers include, for example, polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid, etc. Or a copolymer thereof or the like in an amount of less than 50%, and of course, a compound modified with fluorine or silicon can be used in the present invention.

Polyurethane resin is a copolymer obtained by reacting polyisocyanate and polyol,
As the isocyanate component, aromatic diisocyanate,
An aliphatic diisocyanate and an alicyclic diisocyanate may be used alone or in a mixture thereof.
2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,
4-cyclohexane diisocyanate, etc.,
Polyether polyol or polyester polyol is used as the polyol component, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like is used as the polyether polyol, and diol such as ethylene glycol or propylene glycol and adipic acid or sebacine is used as the polyester polyol. 2 such as acid
A reaction product with a basic acid or a ring-opening polymer such as caprolactone is used.

The above-mentioned synthetic polymer solution mainly composed of polyurethane resin, which contains silicon dioxide and a compound having a high affinity with the fiber base cloth, can be prepared by a conventional coating method such as knife coater, comma coater or reverse coater. Appropriate coating, but the target is 0.6 kg / cm
^In order to obtain a water pressure resistance of ² or more, the resin film weight is generally 5 g / m ² or more, preferably 10 g, although it depends on the smoothness of the coated surface of the fiber cloth and the air permeability (JIS L-1096 method). It is advisable to adjust the coating amount so that the coating amount is at least / m ² and perform coating.

After the resin liquid composed of the above-mentioned polyurethane-based synthetic polymer is applied to the fiber cloth, in the present invention,
The resin component is wet-solidified by immersing it in water at 30 ° C for 0.5 to 10 minutes. Thereafter, after washing in warm water of 40 to 60 ° C. for 5 to 15 minutes, it is dried by a usual method.

In the present invention, for the purpose of further improving waterproofness, the coated fabric may be subjected to water repellent treatment after wet coating. For the water repellent treatment, the well-known water repellent treatment method that is generally carried out as described above may be adopted. Further, when it is desired to further improve the waterproof performance, a dry film thickness of 0.5 on the wet coating layer of the present invention.
A non-porous polyurethane resin layer or the like having a thickness of about 2 μm may be formed. Since the wet coating layer has high water pressure resistance, the waterproof performance is synergistically improved even with a thin film, and the moisture permeability is not significantly reduced.

[0030]

[Working] As in the case of the moisture-permeable and waterproof coating fabric of the present invention, when the synthetic polymer solution mainly composed of polyurethane resin is applied at the time of its production, it is substantially non-porous and has an average particle size of 0.1 μm.
If the following silicon dioxide fine powder and an isocyanate compound, which is a compound having a high affinity for fiber cloth, and at least one resin selected from polyamide resin, polyurethane resin, and polyester resin are contained, Many fine pores are formed at the boundary between the silicon dioxide fine powder and the resin solution at the time of wet solidification of the coating, and excellent waterproofness is obtained because of the fine pores, and excellent moisture permeability is obtained because of the large number of pores. Due to the presence of a compound having a high affinity with the fiber cloth, when the resin solution is wet coagulated, the above-mentioned compound and the resin such as polyamide resin, polyurethane resin, polyester resin, etc. are dissolved at the interface between the resin film and the fiber base cloth. Since the single fibers constituting the fiber base cloth are adhered so as to cover each of them, the peel strength of the film is increased and excellent peel resistance performance is obtained. It made.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The performance of the coated fabrics in the examples was measured by the following method. (1) Water pressure resistance JIS L-1092 (high water pressure method) (2) Water vapor transmission rate JIS L-1099 (A-1 method) (3) Peel strength A hot melt tape is coated on the coated surface with an iron at 150 ° C in the warp direction. Adhere with JIS L-1089
Measured according to the law.

Example 1 Nylon high multifilament 7 for both warp and weft
Weaving a plain woven fabric using 0 denier 68 filaments with a warp density of 120 yarns / inch and a weft yarn density of 90 yarns / inch,
After scouring and dyeing (manufactured by Mitsubishi Kasei Co., Ltd., acid dye DiacidFast Red3BL 2% owf) in the usual way,
Fluorine-based water repellent emulsion Asahi Guard AG-71
After padding with a 0% (Asahi Glass Co., Ltd.) 5% aqueous solution (35% squeezing ratio) and drying, heat treatment was performed at 160 ° C. for 1 minute. Next, using a calendering machine having a mirror surface roll, calendering was performed under conditions of a temperature of 170 ° C., a pressure of 30 kg / cm ² , and a speed of 20 m / min to obtain a base fabric for coating.

Here, a polyurethane resin solution having a composition shown in the following formulation 1 and a solid content of 25% was applied to the calender surface of the above base cloth at a coating amount of 80 g / m ² using a knife over roll coater, Immediately 4 in water at 15 ° C
The resin component was solidified by immersing it for 0 second, followed by washing in warm water at 50 ° C. for 10 minutes and drying to form a resin layer.

[Formulation 1] Laxkin # 1740 100 parts (Seiko Chemical Co., Ltd., polyurethane resin) Resamine X-100 1 part (Dainichi Seika Chemicals Co., Ltd., isocyanate compound) Aerosil R-974 4 parts (Japan Aerosil Co., Ltd.) Co., Ltd., hydrophobic silicon dioxide fine powder having an average particle size of 0.012 μm) N-methoxymethyl 66 nylon 5 parts N · N-dimethylformamide 22 parts

Next, using a gravure coater, the coated surface is treated to be water repellent, and Asahi Guard AG-710 is used.
16% after gravure coating with 5% aqueous solution of
Heat treatment was carried out at 0 ° C. for 1 minute to obtain a coated fabric of the present invention.

For comparison with the present invention, a coated fabric for comparison (Comparative Example 1) is prepared in exactly the same manner as in this Example except that N-methoxymethyl 66 nylon is omitted from Formulation 1 in this Example. ) Got.

The performances of the present invention and the comparative coated fabric were measured and evaluated, and the results are shown together in Table 1.

[0038]

[Table 1]

As is apparent from Table 1, the coated fabric of the present invention has excellent moisture permeability and waterproof performance as well as excellent peel strength.

Examples 2-3 Warp density 1 using 75 denier 48 cation dyeable polyester filaments for both the warp and the weft.
A plain weave of 15 yarns / inch and weft density of 95 yarns / inch is woven and scoured and dyed by a usual method (manufactured by Mitsubishi Kasei Co., Ltd., cationic dye Diacryl Navy Blue GL-PF 3%
owf), followed by padding (35% squeezing rate) with a 5% aqueous solution of Asahi Guard AG-710 (manufactured by Asahi Glass Co., Ltd.), which is a fluorine-based water repellent emulsion, and drying at 160 ° C. for 1 hour.
Heat treatment was performed for 1 minute. Next, using a calendering machine with a mirror surface roll, the temperature was 180 ° C and the pressure was 30 kg / c.
Calendering is performed under the conditions of m ² and speed of 20 m / min.
A base fabric for coating was obtained.

Here, a polyurethane resin solution having a composition shown in the following formulation 2 and a solid content of 25% was applied to the calender surface of the above base cloth at a coating amount of 80 g / m ² using a knife over roll coater, Immediately 4 in water at 15 ° C
The resin component was solidified by immersing it for 0 second, followed by washing in warm water at 50 ° C. for 10 minutes and drying to form a resin layer.

[Formulation 2] Laxkin # 1740 100 parts (Seiko Chemical Co., Ltd., polyurethane resin) Resamine X-100 1 part (Dainichi Seika Chemicals Co., Ltd., isocyanate compound) Aerosil R-974 4 parts (Japan Aerosil Co., Ltd., hydrophobic silicon dioxide fine powder with an average particle size of 0.012 μm) Desmocol 400 5 parts (Sumitomo Bayer Co., Ltd., polyurethane resin) NN-dimethylformamide 22 parts

Next, using a gravure coater, water-repellent treatment is applied to the coating surface, Asahi Guard AG-710.
16% after gravure coating with 5% aqueous solution of
The coated fabric of the present invention (referred to as Example 2) was obtained by performing a heat treatment at 0 ° C. for 1 minute.

In the same manner as in Example 2 except that 5 parts of polytetramethylene isophthalate was used in place of the desmocoll 400 of the formulation 2, the coated fabric of the present invention (Example 3) was obtained. I got).

For comparison with the present invention (Example 2), the coated fabric for comparison (Comparative Example 2 and Comparative Example 2) was prepared in the same manner as in Example 2 except that Desmocoll 400 was omitted from Formulation 2 in Example 2. I will).

The performances of the present invention and the comparative coated fabric were measured and evaluated, and the results are shown together in Table 2.

[0047]

[Table 2]

As is clear from Table 2, the coated fabric of the present invention has an excellent moisture permeability by adding a compound having a high affinity for the silicon dioxide fine powder and the fiber base fabric to the resin solution of the polyurethane synthetic polymer. It can be seen that, while having waterproofing performance, it also has excellent peel strength.

[0049]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a coated cloth having excellent moisture permeability and waterproof performance as well as excellent peel strength. The coated fabric of the present invention has the merit that it can be manufactured at a low cost in terms of its processing steps and raw materials. The coated fabric of the present invention has excellent performances,
A material suitable for sports clothing.

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Claims (1)

[Claims] 1. A silicon dioxide fine particle having a porous resin layer made of a synthetic polymer mainly composed of a polyurethane resin on a fiber cloth, wherein the resin layer is substantially non-porous and has an average particle size of 0.1 μm or less. Containing 1% by weight or more of powder, 0.1% by weight or more of isocyanate compound, and 5% by weight or more of at least one kind of polyamide resin, polyurethane resin and polyester resin, 7,000 g / m ² / 24 hrs
Water vapor transmission rate of more than 0.6 kg / cm ² and water pressure resistance of 200 or more
A moisture-permeable waterproof coating fabric having a peel strength of 0 g / inch or more.